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The Structure and Properties of Polymers
The Structure and Properties of
Polymers
The Structure and Properties of Polymers

What is a polymer?

• A long molecule made up from lots of small molecules called • monomers.
• A long molecule made up from lots of small molecules called • monomers.
• A long molecule made up from lots of small molecules called • monomers.
   
• A long molecule made
 
• A long molecule made

A long molecule made

up from lots of small
up from lots of small
up from lots of small

up from lots of small

 
molecules called
 

molecules called

 

monomers.

• A long molecule made up from lots of small molecules called • monomers.
 

The Structure and Properties of

Polymers

The Structure and Properties of Polymers monomer polymer

monomer

polymer

The Structure and Properties of Polymers monomer polymer

All the same monomer

Homopolymers

Monomers all same

type (A)

A + A + A + A

-A-A-A-A-

eg poly(ethene) polychloroethene PVC

All the same monomer Homopolymers • Monomers all same type (A) • A + A +

Different monomers to form Copolymers

Different monomers – to form Copolymers • Monomers of two • different types A + B

Monomers of two

different types A + B A + B + A + B

-A-B-A-B-

eg polyamides

polyesters

Copolymerisation

when more than one monomer is used.

An irregular chain structure will result eg

propene/ethene/propene/propene/ethene

Why might polymers designers want to design a polymer in this way?

(Hint) Intermolecular bonds!

The Structure of Polymers (plastics)

Polymers are created by the chemical bonding

of many identical units . These polymers are

specifically made of small units bonded into long chains. Carbon makes up the backbone of the molecule and hydrogen atoms are bonded along the carbon backbone.

The Structure of Polymers (plastics)

Polymers that contain primarily carbon and hydrogen are

classified as organic polymers. Polypropylene and polystyrene are examples of these. Even though the basic makeup of many polymers is

carbon and hydrogen, other elements can also be

involved. Oxygen, chlorine, fluorine, nitrogen, silicon, phosphorous and sulfur are other elements that are found in the molecular makeup of polymers.

Polyvinyl chloride (PVC) contains chlorine.

Nylon contains nitrogen. Teflon contains fluorine.

Polyester and polycarbonates contain oxygen.

The Structure of Polymers (plastics)

There are also some polymers that, instead of having a carbon backbone, have a silicon or

phosphorous backbone and these are considered inorganic polymers.

Natural Polymers

Wool, cotton, linen, hair, skin, nails, rubber, and flesh are all naturally occurring polymers

Most naturally polymers are made of protein or cellulose

Synthetic Polymers

Commonly referred to as plastics pliable, able to be moulded

The bonding process.

When thermoplastic polymers are heated they become flexible. There are no cross-links and the molecules can slide

over each other.

Thermosetting polymers do not soften when heated because molecules are crosslinked together and remain rigid.

Thermoplastics (80%)

Thermoplastics (80%) • No cross links between chains. • Weak attractive forces between chains broken by

No cross links between chains.

Weak attractive forces between chains broken by warming.

Change shape - can be remoulded.

Weak forces reform in new shape when cold.

Thermoplastics

Those which soften on heating and then harden again on cooling

These are called thermoplastic polymers because they keep their plastic properties

These polymer molecules consist of long chains which have only weak bonds between the chains

The bonds between the chains are so weak that they can be broken when

the plastic is heated The chains can then move around to form a different shape

The weak bonds reform when it is cooled and the

thermoplastic material keeps its new shape

Thermosets

Thermosets • Extensive cross-linking formed by covalent bonds. • Bonds prevent chains moving relative to each

Extensive cross-linking formed by covalent bonds.

Bonds prevent chains moving relative to each other.

What will the properties of this type of plastic be

like?

Thermosetting

Those which never soften once they have been moulded These are called thermosetting polymers because once set into a shape, that shape cannot be altered

These polymer molecules consist of long chains which have many strong chemical bonds between the chains

The bonds between the chains are so strong that they cannot

be broken when the plastic is heated

This means that the thermosetting material always keeps its

shape

Addition Polymerisation

When ethene is subjected to high pressure it changes from a gas to a liquid

Liquid ethene (still under high pressure) is heated in the presence of a catalyst (O 2 ), an addition reaction takes place.

For addition polymerisation to occur, the monomer must have a double C bond.

This bond breaks to allow the long chains to form.

Modifying ethene, substituting different functional groups for hydrogen atoms produces other monomers that can be polymerised to make polymers with different properties.

Addition polymerisation

Monomers contain C=C bonds

Double bond opens to (link) bond to next monomer molecule

Chain forms when same basic unit is repeated over and over.

Modern polymers also developed based on

alkynes R-C

C - R’

Addition Polymerisation

A carbon carbon double bond is needed in the monomer

A monomer is the small molecule that makes up the polymer

n

H

H

 
C C
C
C

H

H

 

ethene

high pressure/trace O 2

n H H C C H H ethene high pressure/trace O catalyst n H H C

catalyst

n H H C C H H
n
H
H
C
C
H
H

poly(ethene)

Addition Polymerisation • A carbon – carbon double bond is needed in the monomer • A

Addition Polymerisation

The polymer is the only product Involves the opening out of a double bond The conditions of the reaction can alter the properties of the polymer Reaction proceeds by a free radical mechanism Oxygen often used as the initiator

Addition polymerisation

H

H C C
H
C
C

H

H H H H C C C C H H
H
H
H
H
C
C
C
C
H
H
Addition polymerisation H H C C H H H H H C C C C H
Addition polymerisation H H C C H H H H H C C C C H

Addition polymerisation

Conditions are high pressure and an oxygen initiator (to provide the initial free radical).

Monomer = phenylethene Polymer = poly(phenylethene)

Addition polymerisation • Conditions are high pressure and an oxygen initiator (to provide the initial free

Prediction the repeating unit

This is easy, basically open out the double bond.

Cl H H H H H
Cl
H
H
H
H
H
C C
C
C
Cl H H H H H C C Cl H H H H
Cl H H H H
Cl
H
H
H
H
C Cl C C C
C
Cl
C
C
C
Cl H H H H H C C Cl H H H H C Cl C
Cl H H H H H C C Cl H H H H C Cl C
Cl H H H H H C C Cl H H H H C Cl C
Cl H H H H H C C Cl H H H H C Cl C
Cl H H H H H C C Cl H H H H C Cl C
Cl H H H H H C C Cl H H H H C Cl C

chloroethene

poly(chloroethene) aka

polyvinylchloride (pvc)

Linear polymers with side branches

Linear polymers are those in which the main backbone is unbranched.

The way in which side branches are arranged on linear polymers (polypropylene) can affect the properties of the polymer.

Linear polymers with side branches

Isotactic

Same side of the linear

polymer

Greater effect of dispersion forces therefore high density, rigid and

tough and a high softening

temp.

Linear polymers with side branches • Isotactic – Same side of the linear polymer – Greater
Linear polymers with side branches • Isotactic – Same side of the linear polymer – Greater

Atactic

Irregular points on both sides of the linear polymer Chains of molecules cannot get close together, therefore low density. Soft, waxy little use

Linear polymers with side branches • Isotactic – Same side of the linear polymer – Greater

Poly(propene)

This varying degree of randomness will affect the strength and melting point of the polymer.

The less random, the stronger the polymer and the higher the melting point

This is because in a more ordered polymer they chains can get closer together and hence

the van der Waal’s forces will be greater.

Linear polymers with cross links

Cross links are covalent bonds that can form between polymer chains.

If the number of crosslinks is small an elastomer (vulcanised rubber) will result.

If the number of crosslinks is large a hard inflexible thermosetting polymer will be produced.

Linear polymers with cross links • Cross links are covalent bonds that can form between polymer

Linear polymers with cross links

To make a thermosetting polymer, the linear chains are produced first

The cross linking is brought about either by heat or by adding a chemical to react between

the lateral functional groups linking the chains

together.

Araldite is a good example of a two part glue the 2 nd method of producing a thermosetting polymer.

Condensation Polymers

Condensation polymerisation uses monomers

that have two functional groups per molecule.

These are said to be difunctional.

Polymerisation occurs when these monomers react ‘head-to-tail’ to form a new bond that will eventually join the monomers together

A small molecule (often water) is eliminated

Condensation Polymers

Suitable functional groups

-NH2

amine

-OH alcohol

-C

O

O

carboxyl

-C

O

-C O

acid chloride

 
• -C O carboxyl -C O acid chloride OH Cl
• -C O carboxyl -C O acid chloride OH Cl
 

OH

Cl

Condensation Polymers

Involves 2 monomers that have different functional groups.

They also involve the elimination of water or another

small molecule. Hence the term condensation polymer.

Monomer A + Monomer B Polymer + small molecule (normally water).

Common condensation polymers include polyesters

(the ester linkage) and polyamides (the amide linkage as in proteins).

May be natural (protein, starch, cotton, wool, silk) or synthetic (viscose, nylon, polyester)

Polyesters

The OCR example here is terylene, a polymer of

benzene-1,4-dicarboxylic acid and ethane-1,2-diol.

The ester linkage is formed between the monomers

C O
C
O

O the ester linkage

C O O the ester linkage

Polyesters

The structures of other polyesters

n

HO

+ O C OH O C
+
O
C
OH
O
C

n

HO CH 2 CH 2

OH

heat with

an acid

catalyst

O C
O
C
O C O CH 2
O
C O CH 2
n

n

CH 2 O

poly(ethan- 1,2- diyl benzene- 1,4- dicarboxylate)

Polyamides

These involve the linkage of two monomers through

the amide linkage as in proteins (e.g. silk)

 

O

 

C

C N

N

 
 

H

O C N H the amide linkage

the amide linkage

Nylon 6,6 a polyamide

O C HO N H H
O
C
HO
N
H
H

H

 
H N (CH 2 ) 6 H
 

N

(CH 2 ) 6

H

H

(CH 2 ) 4

C
C

O

OH

1,6- diaminohexane

hexanedioic acid

H N
H
N

(CH 2 ) 6

N O C
N
O
C

H

(CH 2 ) 4

O C
O
C

part of a nylon polymer chain

Kevlar a polyamide

H 2 N

H 2 N NH 2 C O HO (CH 2 ) 4 C O OH N

NH 2

C O HO (CH 2 ) 4 C O OH
C
O
HO
(CH 2 ) 4 C
O
OH
N H
N
H
N H O C
N
H
O
C

(CH 2 ) 4

O C
O
C

part of the kevlar polymer chain

Uses of polyamides

The main use of polyesters and polyamides is as

fibres in clothing.

Most clothing now has a degree of manufactured fibres woven into the natural material (such as cotton).

This gives the material more desirable

characteristics, such as stretchiness, and better washability.

Don’t forget that proteins are also polyamides, you

must know how the linkage works with natural

polymers such as proteins.

Addition Polymers

PVC, Teflon, Polystyrene

Addition Polymers

Ethene can be polymerised to produce both low and high density polyethene (commonly known as polyethylene)

LDPE produced with high temp and high pressure long side chains low density (plastic bags)

Soft, flexible and translucent with a waxy surface that repels water.

HDPE produced with lower temp and pressure very few short branches dispersion forces more effective high density (plastic bottles)

Rigid, stronger and more opaque than LDPE

– – Slightly flexible, waxy surface that repels water

Addition Polymers

Rubber is an addition polymer that occurs naturally

The monomer in natural rubber is isoprene. It polymerises to form long chains.

Molecular formula (C 5 H 8 ) n Rubber still contains double bonds which can be attacked by oxygen and can perish

(unlike polythene)

Addition Polymers

Rubber

not elastic long chains straighten out when stretched and remain this way

Susceptible to temperature changes brittle when cold and sticky when hot.

Vulcanisation improved durability and elasticity of rubber.

The linear chains are cross linked using heat and sulfur

Condensation Polymers

Nylon

Can be extruded when molten to form fibres or sheets of strong, durable and elastic material

Its invention had a great impact on the textile and clothing industries.

Condensation Polymers

Nylon 6 : 6

Nylon is a linear chain containing up to 100 repeated units.

The name nylon 6 : 6 refers to the existence of 6 carbon atoms on each of the units

Condensation Polymers • Nylon 6 : 6 – Nylon is a linear chain containing up to

Condensation Polymers

PET plastic Polyethene terephthalate.

Soft drink bottles An example of a polyester

Note the removal of H 2 O (condensation polymer)

Condensation Polymers • PET plastic Polyethene terephthalate. Soft drink bottles An example of a polyester –
Condensation Polymers • PET plastic Polyethene terephthalate. Soft drink bottles An example of a polyester –

Polymer Selection

Due to their versatility, polymers can be produced for almost any imagined purpose.

A huge range of polymers exist today and are used for many different applications.

Their versatility has made them one of them one of the most useful classes of substances

that we rely on in today’s society.

This versatility can be attributed to the many different ways that they can be modified

Recycling

  • Most plastics are produced from crude oil, coal or gas.

  • Many of them are not biodegradable and have become a visible part of our environmental litter.

Recycling  Most plastics are produced from crude oil, coal or gas.  Many of them